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WO2023037848A1 - Composition de conversion ascendante de photons, film, produit transparent supprimant la myopie, et procédé de conversion de lumière visible en lumière ultraviolette - Google Patents

Composition de conversion ascendante de photons, film, produit transparent supprimant la myopie, et procédé de conversion de lumière visible en lumière ultraviolette Download PDF

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WO2023037848A1
WO2023037848A1 PCT/JP2022/031415 JP2022031415W WO2023037848A1 WO 2023037848 A1 WO2023037848 A1 WO 2023037848A1 JP 2022031415 W JP2022031415 W JP 2022031415W WO 2023037848 A1 WO2023037848 A1 WO 2023037848A1
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compound
group
photon upconversion
coumarin
ring
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Japanese (ja)
Inventor
伸浩 楊井
信夫 君塚
直幸 原田
陽一 佐々木
雅記 宇治
ビブヒサン ロイ
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Kyushu University NUC
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Kyushu University NUC
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Priority to EP22867170.7A priority Critical patent/EP4400558A4/fr
Priority to JP2023546860A priority patent/JPWO2023037848A1/ja
Priority to KR1020247007982A priority patent/KR20240056513A/ko
Priority to CN202280061094.6A priority patent/CN117980438A/zh
Priority to US18/690,338 priority patent/US20250340777A1/en
Publication of WO2023037848A1 publication Critical patent/WO2023037848A1/fr
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds

Definitions

  • the present invention relates to a photon upconversion composition useful as a source for generating ultraviolet light, a film using the photon upconversion composition, a myopia-suppressing transparent product, and a method for converting visible light into ultraviolet light.
  • Photon up-conversion is a technology that converts low-energy light into high-energy light, and is attracting attention as an energy creation technology that can improve the efficiency of solar cells, photocatalysts, and other solar-powered devices.
  • a photon upconversion composition is known in which a donor functioning as a sensitizer and an acceptor functioning as a light emitter are combined.
  • a donor functioning as a sensitizer and an acceptor functioning as a light emitter are combined.
  • intersystem crossing occurs to an excited triplet state, and the triplet energy is transferred to the acceptor.
  • the triplet between the two molecules meets and triplet-triplet annihilation occurs, and one of them becomes an excited singlet with higher energy than the excited triplet state. It transitions to the term state and emits light (photon upconversion light emission).
  • the photon upconversion mechanism by such triplet-triplet annihilation can convert irradiated light into light with higher energy (light with a shorter wavelength).
  • Conventional photon up-conversion compositions mainly use donor compounds containing heavy metals such as the iridium complexes described below. is difficult, there is a problem that it is difficult to use industrially.
  • the visible light absorption of the donor is weak, while the reabsorption of photon upconversion light (UC light) is large. There is a limit to the improvement of the conversion efficiency (UC efficiency) of .
  • Non-Patent Document 1 proposes a heavy metal-free photon upconversion composition using BCA as a donor and 2,6-di-tert-butylnaphthalene (DTB-NPh) as an acceptor.
  • the threshold excitation intensity I th is as high as 1300 mW/cm 2 , which is far from a practical level.
  • the present inventors have made intensive studies with the aim of providing a heavy metal-free photon upconversion composition that exhibits high UC efficiency at low excitation light intensity.
  • a photon upconversion composition containing a compound having a coumarin skeleton and containing no heavy metal [2] The photon upconversion composition according to [1], wherein the compound having a coumarin skeleton has a carbonyl group outside the coumarin skeleton. [3] The photon upconversion composition according to [1] or [2], wherein the compound having a coumarin skeleton has a halogen atom. [4] The photon upconversion composition according to [3], wherein the halogen atom is a bromine atom.
  • a heavy metal-free photon upconversion composition that exhibits high UC efficiency at low excitation light intensity can be realized.
  • FIG. 4 is a diagram for explaining the UC emission mechanism of the photon upconversion composition of the present invention
  • 1 is a UC emission spectrum of a toluene solution (composition 1) in which compound A1 and compound D1 are dissolved with excitation light of 445 nm.
  • 4 is a graph showing excitation light intensity dependence of UC efficiency of a toluene solution (composition 1) in which compound A1 and compound D1 are dissolved.
  • 2 is a log-log graph showing excitation light intensity dependence of UC emission intensity of a toluene solution (composition 1) in which compound A1 and compound D1 are dissolved.
  • 4 is a graph showing the difference in excitation light intensity dependence of UC emission intensity with and without a microlens array.
  • the present invention will be described in detail below. Although the constituent elements described below may be described based on representative embodiments and specific examples, the present invention is not limited to such embodiments.
  • the numerical range represented by "-" means a range including the numerical values described before and after "-" as lower and upper limits.
  • the isotopic species of the hydrogen atoms present in the molecule of the compound used in the present invention is not particularly limited. (deuterium D).
  • the photon upconversion composition of the present invention contains a compound having a coumarin skeleton and does not contain heavy metals.
  • the "compound having a coumarin skeleton” in the present invention may be referred to as a "coumarin compound”.
  • "Heavy metals” in “free of heavy metals” in the present invention mean metals having a specific gravity of 4 g/cm 3 or more. "Contains no heavy metals” means that it does not substantially contain heavy metals in any form, either heavy metals as constituent elements of the compound or simple heavy metals, and excludes the inclusion of heavy metals as unavoidable impurities. not something to do.
  • the “photon upconversion composition” in the present invention means a composition that exhibits the ability to convert the light (irradiation light) with which the composition is irradiated into light with a shorter wavelength.
  • the source light to be converted into “shorter wavelength light” is light that excites the coumarin compound contained in the photon upconversion composition, and is preferably light in a longer wavelength region than the ultraviolet region, and visible Light is more preferred.
  • the “exciting light” can be selected from light in which the wavelength range of the emission peak overlaps with the wavelength range in which the target substance to be excited exhibits light absorption. called “excitation light”.
  • the "shorter wavelength light” to be converted is preferably ultraviolet light. That is, a preferred embodiment of the "photon upconversion composition” of the present invention is a composition exhibiting the ability to convert visible light into ultraviolet light.
  • visible light in this specification means light having a wavelength in the range of more than 400 nm and 800 nm or less
  • “ultraviolet light” means light having a wavelength in the range of 200 nm or more and 400 nm or less.
  • the source light and the ultraviolet light included in the destination light may be single light or composite light including a plurality of lights with different emission maximum wavelengths.
  • the light to be converted may include visible light and light other than visible light
  • the light to be converted may include ultraviolet light and light other than ultraviolet light.
  • the photon upconversion composition converts irradiation light (excitation light) into light with a shorter wavelength and emits light, which is referred to as “photon upconversion luminescence” or “UC luminescence”.
  • the light emitted by conversion light emission (light with a shorter wavelength than the irradiation light) is called “UC light”
  • the conversion efficiency of irradiation light into UC light is called “up-conversion efficiency" or "UC efficiency”.
  • the photon upconversion composition of the present invention may be simply referred to as "the composition of the present invention”.
  • the photon upconversion composition of the present invention contains a coumarin compound, it exhibits high UC efficiency at low excitation light intensity while being free of heavy metals. This is presumed to be due to the following mechanism. That is, when the photon upconversion composition of the present invention is irradiated with light, the coumarin compound absorbs the irradiated light and is excited to an excited singlet state, and the excited singlet state changes to an excited triplet state. It is presumed that the crossing efficiently produces triplet energy. Therefore, even at low excitation light intensity, photon upconversion luminescence due to triplet-triplet annihilation is efficiently generated to exhibit high UC efficiency.
  • the fact that the luminescence obtained from the composition is photon upconversion luminescence due to triplet-triplet annihilation means that the lifetime of photon upconversion luminescence is delayed fluorescence of the order of milliseconds to 10 ⁇ 1 milliseconds. This can be confirmed by the fact that the slope changes from 2 to 1 in the double-logarithmic plot of the excitation light intensity dependence of the photon upconversion emission intensity.
  • alkyl group and “aryl group” in the following description are substituents within the following ranges.
  • the “alkyl group” may be linear, branched or cyclic.
  • the number of carbon atoms is preferably 1-20, more preferably 1-10, still more preferably 1-6.
  • Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group and isopropyl group, but the "alkyl group” is not limited to these specific examples.
  • At least one hydrogen atom of an alkyl group may be substituted with a substituent.
  • the "aryl group” may be composed of a monocyclic aromatic ring, may be composed of a condensed ring in which two or more aromatic rings are condensed, or may be composed of a linked ring in which two or more aromatic rings are linked. may be When two or more aromatic rings are linked, they may be linked in a straight chain or may be linked in a branched form.
  • the number of carbon atoms in the aromatic ring constituting the aryl group is preferably 6 to 22, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. preferable.
  • aryl group examples include a phenyl group, a naphthalenyl group, and a biphenyl group, but the "aryl group” is not limited to these specific examples. At least one hydrogen atom of the aryl group may be substituted with a substituent.
  • the coumarin compound used in the present invention is a compound having a coumarin skeleton represented by the following formula.
  • the numbers around the skeleton indicate the position numbers of the coumarin skeleton.
  • the coumarin compound is preferably a coumarin derivative in which at least one hydrogen atom of the coumarin skeleton is substituted with a substituent.
  • the "substituent" in the coumarin skeleton means an atom or atomic group that replaces a hydrogen atom and bonds to the constituent carbon of the coumarin skeleton.
  • the substituents of the coumarin skeleton are described below.
  • the coumarin compound used in the present invention preferably has a carbonyl group represented by the following formula outside the coumarin skeleton.
  • having a carbonyl group outside the coumarin skeleton means containing a carbonyl group within the substituent of the coumarin skeleton.
  • the coumarin compound may have one or two or more carbonyl groups outside the coumarin skeleton.
  • those carbonyl groups may be contained within the same substituent group, or within different substituent groups (substituent groups at different positions inside) may be included respectively.
  • substituents containing two or more carbonyl groups include substituents having a dione structure represented by the following formula.
  • the carbonyl group contained in the substituent may be bonded to the constituent carbon of the coumarin skeleton with a single bond at one of the bonding positions *, or a linking group may be attached to the constituent carbon of the coumarin skeleton at one of the bonding positions *.
  • a linking group may be attached to the constituent carbon of the coumarin skeleton at one of the bonding positions *.
  • a hydrogen atom of an alkylene group, a phenylene group, an ethenylene group, and --NH-- may be substituted, and examples of substituents include an alkyl group, an aryl group, and a cyano group.
  • substituents include an alkyl group, an aryl group, and a cyano group.
  • a hydrogen atom may be bonded to the other bonding position ** of the carbonyl group, or another atom or atomic group may be bonded.
  • Atoms can include halogens, and atomic groups can include alkoxy groups, alkyl groups, amino groups, alkylamino groups, phenylamino groups, pyridyl groups, and hydroxyl groups.
  • the alkoxy group and alkyl group may be linear, branched or cyclic.
  • the alkoxy group and the alkyl group preferably have 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.
  • Specific examples of alkoxy groups include methoxy, ethoxy, n-propoxy and isopropoxy groups, and specific examples of alkyl groups include methyl, ethyl, n-propyl and color propyl groups. can be done.
  • the substitution position of the carbonyl-containing substituent in the coumarin skeleton is not particularly limited, but is preferably at least the 3-position.
  • the coumarin compound may have one or more halogen atoms.
  • the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom, and bromine atom is preferred.
  • those halogen atoms may be the same or different from each other.
  • the halogen atom possessed by the coumarin compound may be introduced as a substituent into the coumarin skeleton or may be contained as a part of the substituent.
  • a halogen atom is preferably bonded to the constituent carbon via a single bond.
  • substituent containing a halogen atom examples include a halogenated alkyl group, a trifluoromethyl group, and a bromophenyl group.
  • alkyl group substituted with a halogen atom in the "halogenated alkyl group” the above description of the "alkyl group” can be referred to.
  • a substituent partially containing a halogen atom may contain one halogen atom, or may contain two or more halogen atoms.
  • the position of the halogen atom or the substituent containing a halogen atom in the coumarin skeleton is not particularly limited.
  • the substitution positions may be at least the 6-position, at least the 8-position, or at least the 6- and 8-positions.
  • the coumarin compound preferably has a tertiary amino group.
  • substituents constituting the tertiary amino group include alkyl groups and aryl groups.
  • the tertiary amino group is preferably a dialkylamino group, a diarylamino group or an alkylarylamino group, more preferably a dialkylamino group.
  • two alkyl groups of the dialkylamino group may be the same or different.
  • Two aryl groups in the diarylamino group may be the same or different.
  • the substituent of the tertiary amino group may be further substituted with a substituent.
  • substituents include alkyl groups and aryl groups.
  • the number of tertiary amino groups possessed by the coumarin compound may be one or two or more. When the coumarin compound has two or more tertiary amino groups, those tertiary amino groups may be the same or different. Further, the tertiary amino group possessed by the coumarin compound may be introduced as a substituent into the coumarin skeleton, or may be contained as a part of the substituent. , It is preferable that a tertiary amino group is bonded to a constituent carbon of the coumarin skeleton with a single bond.
  • substituent containing a tertiary amino group as a part examples include an alkyl group substituted with a tertiary amino group and an aryl group substituted with a tertiary amino group.
  • alkyl group substituted with a tertiary amino group and an aryl group substituted with a tertiary amino group For the description and preferred range and specific examples of the alkyl group of "an alkyl group substituted with a tertiary amino group” and the aryl group of "an aryl group substituted with a tertiary amino group", the above “alkyl group", " The description of "aryl group” can be referred to.
  • a substituent containing a tertiary amino group as part thereof may contain one tertiary amino group, or may contain two or more tertiary amino groups.
  • a hydrogen atom in the coumarin skeleton may be substituted with a substituent other than a carbonyl group-containing substituent, a halogen atom, or a tertiary amino group.
  • substituents include primary amino groups, secondary amino groups, thiocarbonyl groups, halogenated alkyl groups (e.g. trifluoromethyl groups), hydroxyl groups, alkyl groups, cyano groups, imine groups, benzothiazole groups, benzoxazole groups. group, benzimidazole group, furan group, pyrrole group, thiophene group, oxazole group, imidazole group and thiazole group.
  • a ring may be condensed on the coumarin skeleton.
  • the ring condensed to the coumarin skeleton may be either an aromatic ring or an alicyclic ring.
  • rings that can be condensed to the coumarin skeleton include a benzene ring, a polycyclic aromatic ring formed by condensing two or more benzene rings (e.g., naphthalene ring, anthracene ring), cyclohexadiene ring, cyclohexene ring, cyclopentaene ring, and dihydrofuran.
  • heterocyclic ring for example, furan ring, pyrrole ring, thiophene ring, oxazole ring, imidazole ring, thiazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, piperidine ring, pyrrolidine ring, two or more of these condensed ring
  • BODIPY ring boron-dipyrromethene ring
  • the "coumarin skeleton" as used in the present invention includes not only coumarin skeletons in which the 1-position is an oxygen atom and the 2-position is a carbonyl group, but also skeletons in which the oxygen atom at the 1-position is substituted with a sulfur atom, A skeleton in which the carbonyl group at the position is substituted with a thiocarbonyl group and a skeleton in which the oxygen atom at the 1-position of coumarin is substituted with a sulfur atom and the carbonyl group at the 2-position is substituted with a thiocarbonyl group are also included. Preferred are coumarin skeletons.
  • a coumarin compound may have one or two or more coumarin skeletons.
  • the presence or absence of a substituent at each position of the coumarin skeletons and the type of substituent may be the same or different.
  • the coumarin skeletons are preferably linked by a linking group containing a carbonyl group.
  • the number of carbonyl groups contained in the linking group may be one or two or more.
  • a preferable example of the coumarin compound is a compound having a structure in which two coumarin skeletons are linked by a carbonyl group, and a more preferable example is a structure in which the 3-positions of the two coumarin skeletons are linked by a carbonyl group. can be mentioned.
  • the coumarin compound used in the present invention preferably has a structure represented by the following general formula (1).
  • R 1 to R 6 each independently represent a hydrogen atom or a substituent.
  • R 1 to R 6 may be the same or different.
  • preferred ranges, and specific examples of the substituents that R 1 to R 6 can take see the above descriptions of the substituents of the coumarin skeleton and the atoms and atomic groups bonded to the bonding positions ** of the carbonyl group. can be done.
  • Adjacent two of R 1 and R 2 and R 2 to R 5 may be bonded to each other to form a ring.
  • preferred range, and specific examples of the ring formed by combining R 1 to R 5 with each other the above description of the ring that can be condensed to the coumarin skeleton can be referred to.
  • the coumarin compound is a compound of general formula (2) in which at least R 3 and R 5 are hydrogen atoms, and in another aspect of the invention, the coumarin compound is a compound of general formula (1) with R 3 and at least one of R 5 is a halogen atom.
  • the halogen atom is preferably a bromine atom.
  • R 4 in general formula (1) is preferably a tertiary amino group, and R 6 is preferably an alkoxy group.
  • the description of the tertiary amino group described as the substituent of the coumarin skeleton can be referred to. can refer to the description of the carboxy group bonded to the bonding position ** of the above carbonyl group.
  • the coumarin compound used in the present invention also preferably has a structure represented by the following general formula (2).
  • R 1 to R 20 each independently represent a hydrogen atom or a substituent.
  • R 1 to R 20 may be the same or different.
  • preferred ranges, and specific examples of substituents that R 1 to R 20 can take the above description of the substituents of the coumarin skeleton can be referred to.
  • Adjacent two of R 11 and R 12 and R 12 to R 15 , and adjacent two of R 16 and R 17 and R 17 to R 120 may be bonded to each other to form a ring.
  • the description of the ring formed by combining R 11 to R 20 together the description of the ring that can be condensed to the coumarin skeleton can be referred to.
  • the coumarin compound is a compound in which at least R 13 , R 15 , R 18 and R 20 in general formula (2) are hydrogen atoms.
  • the coumarin compound is A compound in which at least one of R 13 and R 15 in general formula (2) is a halogen atom, and in still another aspect of the present invention, the coumarin compound is is a halogen atom and at least one of R 18 and R 20 is a halogen atom.
  • the halogen atom is preferably a bromine atom.
  • At least one of R 14 and R 19 in formula (2) is preferably a tertiary amino group, more preferably both R 14 and R 19 are tertiary amino groups.
  • the compound represented by general formula (2) may or may not have an axisymmetric structure. That is, each combination of R 11 and R 16 , R 12 and R 17 , R 13 and R 18 , R 14 and R 19 , and R 15 and R 20 may have the same structure, At least one of these combinations may have different structures.
  • the photon upconversion composition of the present invention may contain only one compound selected from the group of compounds having a coumarin skeleton (coumarin compounds), or may contain two or more compounds.
  • the photon upconversion composition of the present invention may contain a coumarin compound and a component other than the coumarin compound (a component having no coumarin skeleton, hereinafter referred to as "other components").
  • Other components include, for example, an acceptor compound that receives energy obtained by absorption of light by a coumarin compound and generates photon upconversion luminescence by triplet-triplet annihilation.
  • a photon upconversion composition when a photon upconversion composition includes an acceptor compound, the coumarin compound included in the composition is referred to as the "donor compound.”
  • the acceptor compound In a photon upconversion composition containing a donor compound and an acceptor compound, photon upconversion luminescence due to triplet-triplet annihilation is presumed to occur, for example, by the mechanism shown in FIG. The mechanism of this UC light emission will be described below.
  • the acceptor compound has its lowest excited singlet energy level S 1,A higher than the lowest excited triplet energy level S 1,D of the donor compound, and its lowest excited triplet energy level T 1,A be lower than the lowest excited triplet energy level T 1,D of the donor compound.
  • excitation light for the donor compound is used as irradiation light for the composition.
  • ISC indicates intersystem crossing
  • TET indicates triplet energy transfer from the donor compound to the acceptor compound
  • TTA indicates triplet-triplet annihilation.
  • triplet-triplet annihilation occurs when the triplet molecules of the two molecules meet, and one of them is in the excited singlet state (S 1,A ). That is, photon upconversion occurs due to triplet-triplet annihilation of the acceptor molecule.
  • the acceptor molecule thus brought into an excited singlet state emits fluorescence (UC light) and is deactivated, whereby the composition emits UC light.
  • the excited singlet state (S 1,A ) generated by photon upconversion due to triplet-triplet annihilation has a very high energy level.
  • UC light with high energy (short wavelength) can also be obtained.
  • the coumarin compound used as the donor compound as described above preferably satisfies at least one of the following conditions (A) and (B), and more preferably satisfies both the following conditions (A) and (B).
  • a compound that satisfies the conditions (A) and ( B ) can efficiently absorb the irradiation light, but does not absorb the UC light. can be lower and the UC efficiency can be higher.
  • the “threshold excitation intensity I th ” is the excitation light intensity at the inflection point of the log-log graph showing the excitation light intensity dependence of the UC emission intensity, and is the excitation light intensity required to maximize the UC efficiency. Corresponds to strength. It means that the lower the threshold excitation intensity I th is, the higher the UC efficiency can be obtained with the lower excitation light intensity.
  • “high absorbance” means that the absorbance coefficient is 50,000 M -1 m -1 or more.
  • “low absorbance” means that the absorbance coefficient is 40,000 M -1 cm -1 or less.
  • the acceptor compound used in the photon upconversion composition of the present invention is preferably a compound that satisfies the following condition (C).
  • C having the lowest excited singlet energy level S 1,A higher than the lowest excited singlet energy level S 1, D of the donor compound and higher than the lowest excited triplet energy level T 1,D of the donor compound; Having a low lowest excited triplet energy level T 1,A .
  • the molecule of the acceptor compound that satisfies the condition (C) has the lowest excited singlet energy level S 1,A higher than the lowest excited singlet energy level S 1 ,D of the donor compound.
  • the molecule of the acceptor compound that satisfies the condition (C) has the lowest excited triplet energy level T 1,A lower than the lowest excited triplet energy level T 1, D of the donor compound. can easily receive the excited triplet energy of Thereby, the mechanism of UC light emission shown in FIG. 1 can be operated more reliably.
  • the difference (S 1,A ⁇ S 1,D ) between the lowest excited singlet energy level S 1,A of the acceptor compound and the lowest excited singlet energy level S 1, D of the donor compound is 0.3 to 2 eV. It is preferably 0.4 to 1 eV, more preferably 0.4 to 0.8 eV.
  • the difference (T 1,D ⁇ T 1,A ) between the lowest excited triplet energy level T 1,D of the donor compound and the lowest excited triplet energy level T 1, A of the acceptor compound is 0.01 to 1 eV. preferably 0.01 to 0.5 eV, even more preferably 0.01 to 0.2 eV.
  • the method for measuring the lowest excited singlet energy levels S 1,A , S 1,D and the lowest excited triplet energy levels T 1,A , T 1,D is described below (Lowest excited singlet energy level S 1 and the method for measuring the lowest excited triplet energy level T 1 ). These energy levels can also be obtained by calculation using the density functional theory.
  • the acceptor compound is a compound having a condensed ring in which an aromatic ring and a heterocyclic ring are condensed (however, the total number of rings present in the molecule of the compound is 2 to 5, and the molecule of the compound does not contain a coumarin ring). and substituted polycyclic aromatic hydrocarbon compounds can be used.
  • a compound having a condensed ring in which an aromatic ring and a heterocyclic ring are condensed is sometimes referred to as a “polycyclic aromatic hetero compound”.
  • substituted polycyclic aromatic hydrocarbon compound means a polycyclic aromatic hydrocarbon compound in which at least one hydrogen atom is substituted with a substituent, and a polycyclic Substituents on the structure are not limited to hydrocarbons. Preferred are substituted naphthalene compounds and substituted pyrene compounds.
  • the photon upconversion composition may contain, as an acceptor compound, one compound selected from the group of compounds consisting of polycyclic aromatic heterocompounds and substituted polycyclic aromatic hydrocarbon compounds, or two or more It may contain a compound.
  • the acceptor compound is substituted with a substituent containing at least one selected from the group consisting of an alkynyl group, a substituted silyl group, a benzene ring, a heteroaromatic ring, a cyano group and a halogen atom. It is a compound other than a naphthalene compound.
  • At least one hydrogen atom of the condensed ring of the polycyclic aromatic hetero compound used as the acceptor compound may be substituted with a substituent.
  • the "total number of rings" in the above "the total number of rings present in the molecule of the compound is 2 to 5" is the total number of rings constituting the condensed ring. and the total number of rings contained in the substituents.
  • the total number of rings is five.
  • the aromatic ring constituting the condensed ring of the polycyclic aromatic hetero compound may be an aromatic ring composed of carbon atoms and hydrogen atoms (aromatic hydrocarbon ring), or an aromatic ring containing a hetero atom (aromatic heterocyclic ring ).
  • a benzene ring can be mentioned as an aromatic-hydrocarbon ring.
  • a nitrogen atom, an oxygen atom, and a sulfur atom can be mentioned as the heteroatom constituting the aromatic heterocycle, and a nitrogen atom is preferable.
  • the heteroatom contained in the aromatic heterocycle may be one or two or more. When the heteroaromatic ring contains more than one heteroatom, those heteroatoms may be the same or different.
  • a preferable example of the aromatic heterocycle is a nitrogen-containing aromatic heterocycle having 5 or 6 ring members, and 1 to 3 of the ring members are nitrogen atoms, and more preferable examples are 6 ring members.
  • Specific examples of aromatic heterocycles include pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring and triazine ring.
  • the heterocyclic ring constituting the condensed ring of the polycyclic aromatic heterocycle compound may be either an aromatic heterocyclic ring or an alicyclic heterocyclic ring.
  • a nitrogen atom, an oxygen atom, a sulfur atom, and a cerium atom can be mentioned as a heteroatom constituting the heterocyclic ring.
  • the heteroatom contained in the heterocyclic ring may be one or two or more. When a heterocycle contains more than one heteroatom, the heteroatoms may be the same or different.
  • the heterocyclic ring has 5 or 6 ring members, and preferably 1 to 3 of the ring members are heteroatoms.
  • heterocyclic rings include pyrrole ring, pyrroline ring, pyrazole ring, imidazole ring, triazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, thiophene ring, 2,3-dihydrodiophene ring, furan ring, 2,3-dihydrofuran ring, 1,3-dioxole ring, 2,3-dihydro-1,4-dioxin ring, oxazole ring, isoxazole ring, oxadiazole ring, thiazole ring, isothiazole ring, thiadiazole rings, and selenadiazole rings.
  • the number of rings constituting the condensed ring may be any of 2 to 5, preferably 2 or 3. Specific examples of the condensed rings constituting the polycyclic aromatic heterocompounds are shown below, but the polycyclic aromatic heterocompounds that can be used as the acceptor compound in the present invention are limited to those having these condensed rings. not something.
  • substituents are not particularly limited, but examples include alkynyl groups, substituted silyl groups, aryl groups, heteroaryl groups, and cyano groups.
  • alkynyl groups may be linear, branched or cyclic.
  • the alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and still more preferably 2 to 6 carbon atoms.
  • ethynyl group, propynyl group, butynyl group and the like can be exemplified.
  • At least one hydrogen atom of an alkynyl group may be substituted with a substituent.
  • substituents include alkyl groups, halogenated alkyl groups, dialkoxyalkyl groups, substituted silyl groups, aryl groups, and pinacolatoboryl groups.
  • substituted silyl group For the description, preferred range, and specific examples of the substituted silyl group, reference can be made to the description of the substituted silyl group as a substituent of the condensed ring below. Reference can be made to the description of the "aryl group”.
  • An alkyl group as a substituent of an alkynyl group may be linear, branched or cyclic, but preferably linear or branched. The number of carbon atoms in the alkyl group is preferably 1-20.
  • linear alkyl groups include methyl, ethyl and n-propyl groups, as well as long-chain alkyl groups such as dodecyl, tridecyl, tetradecyl, pentadecyl and hexadecyl groups.
  • branched alkyl groups include branched alkyl groups having 3 to 6 carbon atoms such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group and isohexyl. can be mentioned.
  • the halogenated alkyl group as a substituent of the alkynyl group may be a halogenated alkyl group in which all the hydrogen atoms of the alkyl group are substituted with halogen atoms, or a part of the hydrogen atoms of the alkyl group may be substituted with halogen atoms. It may be a substituted, partially halogenated alkyl group.
  • halogenated alkyl group in which all the hydrogen atoms of the alkyl group are substituted with halogen atoms, or a part of the hydrogen atoms of the alkyl group may be substituted with halogen atoms. It may be a substituted, partially halogenated alkyl group.
  • preferred range, and specific examples of the alkyl group substituted with a halogen atom the above description of the "alkyl group" can be referred to.
  • the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom.
  • a dialkoxyalkyl group as a substituent of an alkynyl group preferably has a structure in which two alkoxy groups are bonded to the terminal carbon atom of an alkyl group.
  • the alkyl group that constitutes the "dialkoxyalkyl group” the above description of the "alkyl group” can be referred to.
  • Two alkoxy groups constituting a "dialkoxyalkyl group” may be linear or branched.
  • the number of carbon atoms in the alkoxy group is preferably 1-20, more preferably 1-10, even more preferably 1-6.
  • Specific examples of alkoxy groups include methoxy, ethoxy, n-propoxy and isopropoxy groups.
  • Two alkoxy groups constituting a "dialkoxyalkyl group" may be the same or different.
  • a substituted silyl group as a substituent of the condensed ring may be a mono-substituted silyl group, a di-substituted silyl group or a tri-substituted silyl group, preferably a tri-substituted silyl group.
  • substituents of the substituted silyl group include alkyl groups and aryl groups.
  • the alkyl group may be linear, branched or cyclic, but preferably linear or branched.
  • the number of carbon atoms in the alkyl group may be 1 or more or 2 or more, preferably 2 or more, more preferably 3 or more.
  • the substituted silyl group is a trialkylsilyl group, the total number of carbon atoms of the three alkyl groups is preferably 6 or more.
  • the upper limit of the number of carbon atoms is not particularly limited, it is preferably 20 or less.
  • the above description of the "aryl group” can be referred to.
  • Specific examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group and triphenylsilyl group.
  • a heteroaryl group as a substituent of a condensed ring is preferably composed of a monocyclic aromatic heterocyclic ring. A nitrogen atom, an oxygen atom, and a sulfur atom can be mentioned as a heteroatom constituting the aromatic heterocycle.
  • the heteroatom contained in the aromatic heterocycle may be one or two or more.
  • the heteroaromatic ring contains more than one heteroatom, those heteroatoms may be the same or different.
  • the heteroaryl group has 5 or 6 ring members and is composed of an aromatic heterocyclic ring in which 1 to 3 of the ring members are heteroatoms.
  • Specific examples of the aromatic heterocyclic ring constituting the heteroaryl group include pyrrole ring, imidazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, furan ring, thiophene ring, oxazole ring, and thiazole ring. can be done.
  • At least one hydrogen atom of the heteroaromatic ring may be substituted with a substituent.
  • the positions of the substituents on the condensed ring are not particularly limited, and the number of substitutions may be any number within a range not exceeding the number of substitutable positions.
  • the number of substituents may be selected, for example, from the range of 1 to 4, may be selected from the range of 1 to 3, or may be 1 or 2.
  • the positions of the substituents may be the positions of the benzene ring that have an ortho-position relationship with each other, and the positions that have a meta-position relationship with each other. may also be positioned in a para-position relationship with each other.
  • those substituents may be the same or different.
  • acceptor compound examples include but the acceptor compound that can be used in the present invention should not be construed as limited by these specific examples.
  • the lowest excited singlet energy level S1 of the compound used in the present invention is obtained by putting the compound into a solution, measuring the fluorescence spectrum, and converting the wavelength of the fluorescence peak on the shortest wavelength side into an energy value according to the following conversion formula. be done.
  • the lowest excited triplet energy level T 1 of the compound used in the present invention is obtained by measuring the phosphorescence spectrum of the compound in a solution and converting the wavelength of the phosphorescence peak into an energy value according to the following conversion formula. .
  • the solvent used in dissolving the compound is selected to be capable of dissolving the compound (eg, tetrahydrofuran).
  • the concentration of the solution is such that the spectrum can be measured (for example, 100 ⁇ M).
  • the emission spectrum can be measured using JASCO FP-8300 using a xenon lamp as an excitation light source.
  • Conversion formula: S1 [eV] 1239.85/ ⁇ F
  • Conversion formula: T 1 [eV] 1239.85/ ⁇ P
  • ⁇ F is the fluorescence peak wavelength [nm]
  • ⁇ P is the phosphorescence peak wavelength [nm].
  • the photon upconversion composition contains a coumarin compound (donor compound) and an acceptor compound
  • the molar ratio of the donor compound to the acceptor compound [(number of moles of donor compound/number of moles of acceptor compound) ⁇ 100] is preferably 0. 0.01-20%, more preferably 0.1-10%, even more preferably 1-5%.
  • the concentration of the donor compound can be increased to allow more absorption of the excitation light.
  • the photon upconversion composition of the present invention may further contain other components.
  • other components include solvents that dissolve coumarin compounds (donor compounds) and acceptor compounds, matrix materials such as polymers that hold these compounds in a solid state in a dispersed state, and additives such as surfactants. be able to.
  • Solvents and polymers can be appropriately selected from known ones and used. Examples of solvents include dimethylformamide, tetrahydrofuran, chloroform, toluene, benzene, and mixed solvents thereof.
  • Polymers can include polystyrene, poly(alkyl methacrylates), poly(alkyl acrylates), poly(N-alkyl acrylamides), polyvinyl alcohols, and can also include bioplastics.
  • Bioplastics contain substances derived from renewable organic resources as raw materials, and can be used by appropriately selecting from chemically or biologically synthesized materials. For example, cellulose or protein can be used, and it is particularly preferable to use biodegradable biopolymers. In the present invention, two or more of these polymers may be mixed and used.
  • the polymer may have a glass transition temperature of room temperature (25° C.) or more, or a glass transition temperature of less than room temperature.
  • the film When a polymer having a glass transition temperature of room temperature or higher is used as a matrix material, the film exhibits a hard property, making it difficult for molecular diffusion to occur, and energy is transferred between compound molecules mainly by energy diffusion. In addition, when a polymer having a glass transition temperature lower than room temperature is used as a matrix material, the film exhibits a soft property, so energy may be transferred by molecular diffusion.
  • the glass transition temperature of a polymer can be measured with a differential scanning calorimeter.
  • the method of dispersing the coumarin compound and the acceptor compound in the polymer is not particularly limited. The resulting solution may be dispersed in a polymer.
  • the non-volatile solvent should be a non-volatile liquid that dissolves the compound well, and is appropriately selected from among surfactants (eg Triton R X-100) and low molecular weight organic solvents (eg hexadecane).
  • surfactants eg Triton R X-100
  • low molecular weight organic solvents eg hexadecane
  • the ratio of the coumarin compound to the total composition is preferably 0.00005 to 0.5% by weight, more preferably 0.00005 to 0.05% by weight. It is preferably 0.0005 to 0.03% by weight and more preferably 0.0005 to 0.03% by weight.
  • the ratio of the coumarin compound to the total composition is preferably 0.001 to 1 wt%, more preferably 0.01 to 1 wt%, and 0.01 to 1 wt%. More preferably 1 to 0.5% by weight.
  • the photon upconversion compositions of the present invention exhibit high UC efficiency at low excitation light intensities while being free of heavy metals. Therefore, the photon upconversion composition of the present invention is characterized by its low environmental load, ease of securing stable raw materials, and ease of industrial use.
  • the photon upconversion composition of the present invention can efficiently convert irradiation light such as visible light into ultraviolet light and emit light at a practical level of excitation light intensity. Therefore, the photon upconversion composition of the present invention can be effectively used as an ultraviolet light generation source in various situations where ultraviolet light is used.
  • ultraviolet light can be obtained at low cost by applying the film of the photon upconversion composition of the present invention to a transparent body such as transparent glass or a transparent resin board and exposing it to sunlight.
  • the photocatalyst can be activated with high energy efficiency, and the efficiency of artificial photosynthesis using the photocatalyst can be increased.
  • it can greatly contribute to improving the fuel efficiency of a fuel cell vehicle in which a photocatalyst acts to produce hydrogen from water and sunlight, and the hydrogen is used to generate electricity in a fuel cell.
  • the transparent body to which the film is applied is an object that can transmit at least a portion of UC light (preferably 10% or more, more preferably 50% or more, still more preferably 90% or more, particularly preferably 99% or more). Any object that can transmit at least a portion of UC light in a wavelength region that is particularly desired to be used may be used.
  • the film When the film is applied to the transparent body, it may be applied directly to the surface of the transparent body, laminated on the surface of the transparent body, or laminated on the surface of the transparent body in a detachable state. Alternatively, it may be sandwiched between two transparent bodies.
  • the UC light can be focused to a specific spot by applying a film, and energy can be used more efficiently.
  • violet light of 360 to 400 nm in ultraviolet light has a myopia-suppressing effect.
  • films that emit UC light, including ultraviolet light between 360 and 400 nm can be used for myopia control.
  • the sunlight and indoor light striking the film are converted into ultraviolet light, which is harmful to humans (especially children and students) and animals. It can be effective in suppressing myopia.
  • the film by applying the film to LED lights, smart phones, personal computers, and television displays, the illumination light from these devices is converted into ultraviolet light, which is effective in suppressing myopia of the operator.
  • the photon upconversion composition of the present invention is also useful as a film that serves as a source of such ultraviolet light of 360 to 400 nm.
  • Products exhibiting a myopia-suppressing effect may be produced by applying such a film to a transparent material, or by mixing the coumarin compound of the present invention with a transparent material such as a transparent resin to produce windows, spectacles, goggles, etc. You may manufacture by making into transparent products, such as a contact lens and a translucent plate.
  • the photon upconversion composition of the present invention is applicable to a wide range of transparent products such as films, lenses, and transparent plates, and is useful for manufacturing myopia-suppressing transparent products.
  • transparent as used herein means that at least light of 360 nm to 400 nm and light necessary for the composition of the present invention to cause photon upconversion are transmitted.
  • Films of the present invention comprise photon upconversion compositions of the present invention.
  • the description in the section ⁇ Photon upconversion composition> can be referred to.
  • Embodiments of the film of the present invention include a film formed from the photon upconversion composition and a layer formed from the photon upconversion composition on a substrate. In the latter aspect, the film may be composed only of the layered photon upconversion composition, or the film may be composed of the layered photon upconversion composition and the substrate.
  • the method for forming the photon up-conversion composition into a film is not particularly limited, and known film forming methods such as calendering, extrusion molding, and inflation molding can be used. Also, the method for forming the photon upconversion composition in layers is not particularly limited, and either a dry process or a wet process may be used.
  • the base material is also not particularly limited, and can be made of, for example, glass, transparent plastic, quartz, silicon, or the like.
  • the photon upconversion composition used for the film can be easily formed and formed into a film, and the mechanical properties of the film can be controlled. preferably containing.
  • the polymer used in the composition can be appropriately selected and used from known film polymers, such as polystyrene, poly(alkyl acrylate), poly(alkyl methacrylate), poly(N-alkylacrylamide), epoxy Resin, polyvinyl alcohol, etc. can be mentioned.
  • a hydrophilic polymer such as polyvinyl alcohol
  • the film of photon upconversion composition may be of single-layer or multi-layer construction. When the film is of multilayer construction, it is preferred that at least adjacent layers thereof differ in composition from each other.
  • An embodiment of the film of the present invention also includes an impregnated film in which a porous film is impregnated with a liquid material of a coumarin compound.
  • Liquid materials include a solution in which a coumarin compound is dissolved, a solution in which a coumarin compound (donor compound) and an acceptor compound are dissolved, a melt obtained by heating and melting a coumarin compound, and a mixture of a coumarin compound and an acceptor compound by heating. It is possible to use a melt that is melted by heating.
  • the melt obtained by heating the mixture to a molten state may be a melt of the acceptor compound in which a solid donor compound is dispersed, or may be a melt in which both the acceptor compound and the donor compound are in a molten state.
  • a film impregnated with a solution is preferable because it is easy to obtain a stable product.
  • the porous film an organic porous film in which an organic filler is dispersed in a matrix polymer can be used, and a commercially available product such as a microporous film (manufactured by 3M) can be used.
  • a PTFE membrane film manufactured by Tokyo Glass Instruments Co., Ltd.
  • a polyethylene porous sheet manufactured by Fron Chemical Co., Ltd.
  • a porous film having a pore size of 0.3 ⁇ m or less, preferably 0.2 ⁇ m or less, and more preferably 0.1 ⁇ m or less can be used as the porous film.
  • a porous film having a moisture permeability of 10,000 g/m 2 ⁇ 24 h or more, or a porous film having an air permeability of 200 seconds/100 ml or more can be used.
  • a film that absorbs and retains an organic liquid but does not allow water to permeate can be used as the porous film.
  • the thickness of the film of the present invention is preferably 10 nm to 1 cm, more preferably 100 nm to 500 ⁇ m, even more preferably 1 ⁇ m to 100 ⁇ m.
  • the total thickness is within the above thickness range.
  • the film of the present invention may be composed only of the film containing the photon upconversion composition of the present invention, or may have other layers and films.
  • Other films include oxygen barrier films. When an oxygen barrier film is used, it is preferable to cover and seal the entire film containing the photon upconversion composition with the oxygen barrier film.
  • the oxygen barrier film a film of polyvinyl alcohol or a film of a copolymer of vinyl alcohol and other monomers can be used.
  • an ethylene-vinyl alcohol copolymer film can be preferably used.
  • other layers include a layer having a microlens array.
  • Photon upconversion luminous efficiency can be improved by forming a layer having a microlens array on a film containing the photon upconversion composition of the present invention and irradiating excitation light through the layer having the microlens array.
  • the lens diameter, pitch, and arrangement of the microlens array can be adjusted so as to improve photon upconversion luminous efficiency.
  • the lens diameter that determines the curvature of each arrayed lens can be selected, for example, in the range of 10 ⁇ m or more, 50 ⁇ m or more, or 100 ⁇ m or more, or in the range of 200 ⁇ m or less, 160 ⁇ m or less, or 130 ⁇ m or less.
  • the myopia-suppressing transparent article of the present invention comprises a photon upconversion composition.
  • the transparent product in the "myopia-suppressing transparent product" of the present invention means that at least part of the UC light (preferably 10% or more, more preferably 50% or more, still more preferably 90% or more, particularly preferably 99% or more) is means a permeable product.
  • the photon upconversion composition used in the present invention is preferably a photon upconversion composition that emits UC at least ultraviolet light of 360 to 400 nm.
  • the photon upconversion composition used in the present invention is preferably the photon upconversion composition of the present invention, and the photon upconversion composition of the present invention emits UV light of at least 360 to 400 nm by UC. It is more preferable to have
  • the description in the section ⁇ Photon upconversion composition> can be referred to.
  • the present invention can be applied without any particular limitation as long as it is a transparent product.
  • Specific examples of myopia-suppressing transparent products include glasses, goggles, contact lenses, transparent plates for windows, window glass films, lens cases for LED lights, and displays for smartphones, personal computers, televisions, and the like.
  • the photon up-conversion composition of the present invention to products and specific effects, the corresponding description in the above section [Utility of photon up-conversion composition] can be referred to.
  • the method of converting visible light into ultraviolet light of the present invention is a method of irradiating the photon upconversion composition of the present invention or the film of the present invention with visible light to convert it into ultraviolet light.
  • the photon upconversion composition of the present invention and the definition of visible light and ultraviolet light, reference can be made to the description in the section ⁇ Photon Upconversion Composition> above.
  • the description in the ⁇ Film> section above can be referred to.
  • the photon upconversion composition of the present invention or the film of the present invention is irradiated with visible light.
  • the visible light to be irradiated may be a single light having an emission maximum wavelength at a specific wavelength in the visible region, or may be a composite light obtained by synthesizing a plurality of visible light having different emission maximum wavelengths. Composite light obtained by synthesizing light of continuous wavelengths in the visible region may also be used.
  • the light with which the composition is irradiated may include light other than visible light in addition to visible light. Examples of irradiation sources include sunlight, LEDs, Xe lamps, lasers, and the like.
  • the irradiation intensity is preferably 0.1 to 1000 mW/cm 2 , more preferably 0.5 to 100 mW/cm 2 and even more preferably 1 to 50 mW/cm 2 .
  • the irradiation time is not particularly limited, and may be, for example, 1 minute or longer.
  • irradiation with such visible light causes the photon upconversion composition of the present invention or the film of the present invention to emit ultraviolet light as UC light.
  • This light emission may be recognized in the ultraviolet region (wavelength range of 200 to 400 nm), but it is particularly preferable that the light emission of ultraviolet light is recognized within the range of 360 to 400 nm.
  • ultraviolet light emission is recognized within the range of 360 to 400 nm
  • the maximum emission wavelength of the ultraviolet light is within the range of 360 to 400 nm, or the maximum emission wavelength is in the vicinity of 360 to 400 nm.
  • an emission intensity of 50% or more of the intensity at the emission maximum wavelength is observed at 360 nm or 400 nm.
  • ultraviolet light of 360 to 400 nm exhibits the effect of suppressing myopia. Therefore, ultraviolet light obtained in a manner in which emission of ultraviolet light is observed within this range can be effectively used for suppressing myopia.
  • the fluorescence quantum yield of the coumarin 6 solution the absorbance and emission spectrum of each solution to be measured, the excitation light intensity at the time of measurement, and the refractive index of the solvent are used. (manufactured by Otsuka Electronics: MCPD-9800) was used. Quantaurus-Tau C11367-02/C11567-01 manufactured by Hamamatsu Photonics was used to measure the UC emission lifetime.
  • Donor compounds and acceptor compounds used in Examples The donor compounds and acceptor compounds used in this example are shown below.
  • Table 1 shows the absorption maximum wavelength, emission maximum wavelength, lowest excited singlet energy level S1 and lowest excited triplet energy level T1 of the main absorption peaks of these donor compounds and acceptor compounds.
  • S 1 of the acceptor is a value calculated from the maximum emission wavelength
  • S 1 of the donor is a value calculated from the maximum absorption wavelength
  • T 1 of the acceptor is a value calculated by the density functional theory (DFT)
  • T 1 of the donor is a value calculated from the emission maximum wavelength.
  • the emission maximum wavelength of compounds D1, D2, D3, and D4 is the emission maximum wavelength of phosphorescence measured at a low temperature
  • the T 1 of these compounds is a value calculated from the measured emission maximum wavelength of phosphorescence.
  • Example 1 Preparation and Evaluation of Photon Upconversion Composition Containing Compound D1 and Compound A1
  • Compound D1 and compound A1 were dissolved in toluene in an Ar atmosphere glove box to prepare a toluene solution (composition 1).
  • concentration of compound D1 was 100 ⁇ M and the concentration of compound A1 was 10 mM.
  • FIG. 2 shows the UC emission spectra of the prepared composition 1, which was measured by changing the excitation light intensity in the range of 0.19 mW/cm 2 to 23.0 W/cm 2 .
  • the measurement was carried out in an Ar atmosphere with an excitation light wavelength ⁇ ex of 445 nm and a 425 nm long wavelength cut filter placed between the sample and the spectrometer.
  • the results of measuring the dependence of the UC efficiency on the excitation light intensity are shown in FIG.
  • composition 1 has a UC efficiency ⁇ UC of 15.1%, a threshold excitation intensity I th of 5.51 mW/cm 2 , and a UC emission lifetime ⁇ UC of 0.40 ms (millimeters). seconds). From this result, it was confirmed that composition 1 is free of heavy metals and exhibits high UC efficiency at low excitation light intensity.
  • Example 2 Preparation and evaluation of photon upconversion composition containing compound D2 and compound A1
  • a toluene solution of compound D2 and compound A1 ( Composition 2) was prepared and evaluated for UC properties.
  • composition 2 had a UC efficiency ⁇ UC of 3.4%, a threshold excitation intensity I th of 35.1 mW/cm 2 , and a UC emission lifetime ⁇ UC of 0.26 ms (milliseconds).
  • Example 3 Preparation and evaluation of photon upconversion composition containing compound D3 and compound A1
  • a toluene solution of compound D3 and compound A1 ( Composition 3) was prepared and evaluated for UC properties.
  • composition 3 had a UC efficiency ⁇ UC of 4.36%, a threshold excitation intensity I th of 32.7 mW/cm 2 , and a UC emission lifetime ⁇ UC of 0.35 ms (milliseconds).
  • Example 4 Preparation and evaluation of photon upconversion composition containing compound D4 and compound A1
  • a toluene solution of compound D4 and compound A1 ( Composition 4) was prepared and evaluated for UC properties.
  • composition 4 had a UC efficiency ⁇ UC of 0.16%, a threshold excitation intensity I th of 10.7 W/cm 2 , and a UC emission lifetime ⁇ UC of 0.28 ms (milliseconds).
  • Example 5 Preparation and evaluation of photon upconversion composition containing compound D1 and compound A2
  • a toluene solution of compound D1 and compound A2 ( Composition 5) was prepared and evaluated for UC properties.
  • composition 5 had a UC efficiency ⁇ UC of 18.2%, a threshold excitation intensity I th of 334.4 mW/cm 2 , and a UC emission lifetime ⁇ UC of 0.092 ms (milliseconds).
  • Example 6 Preparation and Evaluation of Encapsulant of Porous Film Impregnated with Photon Upconversion Composition
  • a solution was prepared by dissolving compound D1 and compound A1 in hexyl benzoate in an Ar atmosphere glove box.
  • the concentration of compound D1 was 100 ⁇ M and the concentration of compound A1 was 10 mM.
  • a 38 ⁇ m thick porous film (3M TM microporous film) was immersed in this solution to impregnate the porous film with the solution. After that, the porous film was taken out and sandwiched between two glass substrates for sealing.
  • the porous film used here had a pore diameter of 0.3 ⁇ m or less, a tensile strength of 8 N/cm in both the MD and CD directions, a tensile elongation of 280% in the MD direction and 260% in the CD direction, and air permeability. is 210 sec/100 ml and a film mainly composed of polypropylene with a moisture permeability of 12000 g/m 2 ⁇ 24 h.
  • the UC emission spectrum of the produced sealant was measured while changing the excitation light intensity in the range of 146.3 mW/cm 2 to 6.8 W/cm 2 .
  • Example 7 Preparation and Evaluation of Laminates of Porous Films and Microlens Arrays Impregnated with Photon Upconversion Compositions 38 ⁇ m thick porous films impregnated with hexyl benzoate solutions of Compound D1 and Compound A1 was prepared according to the same procedure as in Example 6. This porous film was placed on a glass substrate, and a 720 ⁇ m-thick synthetic quartz microlens array (lens diameter: 124 ⁇ m) was laminated on the porous film for sealing. In addition, a laminate for comparison was also produced, which was changed only in that a sealing film on which no microlens array was formed was used instead of the microlens array.
  • the prepared laminates were irradiated with excitation light of 445 nm from the microlens array side (sealing film side), and photon upconversion luminescence was detected with a detector.
  • excitation light 445 nm from the microlens array side (sealing film side)
  • photon upconversion luminescence was detected with a detector.
  • the UC emission spectrum was measured by changing the excitation light intensity, it was confirmed that the UC emission intensity in the 350 to 440 nm region increased as the excitation light intensity increased in all laminates.
  • FIG. 5 shows the relationship between excitation light intensity and UC emission intensity. It was confirmed that the UC luminous efficiency can be greatly improved by forming a microlens array.
  • the photon upconversion composition of the present invention exhibits high UC efficiency at low excitation light intensity while being free of heavy metals. Therefore, the photon upconversion composition of the present invention has a small environmental load, and is easy to use industrially because it is easy to secure stable raw materials. can contribute. Therefore, the present invention has high industrial applicability.

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Abstract

L'invention concerne une composition de conversion ascendante de photons sans métal lourd qui comprend un composé ayant un squelette de coumarine et présente une efficacité de conversion ascendante de photons élevée à une faible intensité de lumière d'excitation.
PCT/JP2022/031415 2021-09-10 2022-08-19 Composition de conversion ascendante de photons, film, produit transparent supprimant la myopie, et procédé de conversion de lumière visible en lumière ultraviolette Ceased WO2023037848A1 (fr)

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EP22867170.7A EP4400558A4 (fr) 2021-09-10 2022-08-19 Composition de conversion ascendante de photons, film, produit transparent supprimant la myopie, et procédé de conversion de lumière visible en lumière ultraviolette
JP2023546860A JPWO2023037848A1 (fr) 2021-09-10 2022-08-19
KR1020247007982A KR20240056513A (ko) 2021-09-10 2022-08-19 포톤 업컨버전 조성물, 필름, 근시 억제 투명 제품 및 가시광선을 자외광으로 변환하는 방법
CN202280061094.6A CN117980438A (zh) 2021-09-10 2022-08-19 光子上转换组合物、膜、近视抑制透明产品及将可见光线转换为紫外光的方法
US18/690,338 US20250340777A1 (en) 2021-09-10 2022-08-19 Photon upconversion composition, film, myopia-suppressing transparent product, and method for converting visible light into ultraviolet light

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WO2024122604A1 (fr) * 2022-12-09 2024-06-13 出光興産株式会社 Procédé de production de film organique de conversion ascendante optique, dispositif de production de film organique de conversion ascendante optique et film organique de conversion ascendante optique

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